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WO2018039230A1 - Polymères électrochromes jaunes et orangés à large bande interdite - Google Patents

Polymères électrochromes jaunes et orangés à large bande interdite Download PDF

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Publication number
WO2018039230A1
WO2018039230A1 PCT/US2017/048013 US2017048013W WO2018039230A1 WO 2018039230 A1 WO2018039230 A1 WO 2018039230A1 US 2017048013 W US2017048013 W US 2017048013W WO 2018039230 A1 WO2018039230 A1 WO 2018039230A1
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Prior art keywords
arylalkyl
amino
aryl
amido
alkyl
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John Robert Reynolds
Kangli CAO
Anna M. OSTERHOLM
Dwanleen E. SHEN
Dylan Thomas CHRISTIANSEN
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Georgia Tech Research Institute
Georgia Tech Research Corp
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Georgia Tech Research Institute
Georgia Tech Research Corp
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Priority to EP17844281.0A priority patent/EP3500647A4/fr
Publication of WO2018039230A1 publication Critical patent/WO2018039230A1/fr
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    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
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Definitions

  • Conjugated polymers are used in electrochromic applications, allowing the coloration and redox properties to be tuned through structural design and synthesis.
  • Cathodically coloring cyan, magenta, and yellow electrochromic polymers (ECPs), as well as numerous secondary colors, that switch from a vibrantly colored state to a colorless state upon electrochemical oxidation have been synthesized. These have yielded a broad palette of vibrant colors including browns and blacks that are accessible through blending of ECP solutions.
  • Dioxythiophene (DOT) based polymers have been used in the design of ECPs that undergo their colored-to-clear transition at low oxidation potentials.
  • oxidation of a neutral polymer leads to the formation of cation radicals (polarons) and dications (bipolarons), which give rise to conformational changes of the polymer backbone that affects the polymer's absorption profile.
  • polarons cation radicals
  • bipolarons dications
  • the first cathodically colored yellow-to-transmissive ECP, the alternating copolymer, poly(3,4-propylenedioxythiophene-a//-phenylene) (PProDOT-Ph) was disclosed in Amb et al. US. Patent No. 8,699,603, March 19, 2013. That ECP completed the subtractive color palette, enabling full color electrochromic displays and windows.
  • PProDOT-Ph can be patterned in an electroactive grating to create an artificial chameleon effect, owing to its minimal absorption in the visible and its relatively large change in refractive index during redox switching, as disclosed in Bhuvana et al. Angew. Chem. Int. Ed. 2013, 52,1 180-4.
  • PProDOT-Ph has a relatively high oxidation potential (ca. 1.1 V vs. Fc/Fc + ) for achievement of a fully bleached state, and this high potential can be attributed to the aromaticity of the pTaenylene unit.
  • PProDOT-Ph has the potential for use in blends of ECPs to obtain various color hues or a broadly absorbing black or brown color, the large potential required to bleach the PProDOT-Ph component is beyond the stability limits of more easily oxidizable ECPs in a mixture, decreasing the redox switching stability of electrochromic films.
  • the need for high-gap polymers with sufficiently low electrochemical oxidation potentials to permit highly stable ECPs, particularly those that may be solution processed is an unfulfilled need in the art.
  • the D repeating units for the (D) selected from
  • X is S, Se, O, or NR y is 0 or 1 ; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently H, C1 -C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C 6 -Ci 4 aryl, C7-C30 arylalkyl, C 8 -C 3 o arylalkenyl, C 8 -C 30 arylalkynyl, hydroxy, C 2 -C 3 o alkoxy, C 6 -Ci 4 aryloxy, C7-C30 arylalkyloxy, C2-C30 alkenyloxy, C2-C 0 alkynyloxy, C8-C30 arylalkenyloxy, C8-C30 arylalkynyloxy, CO2H, C2-C30 alkylester, C7-C 15 arylester, C
  • X is S, Se, O, or NR;
  • R, R 9 and R 10 are independently C 3 -C 30 alkyl, C3-C30 alkenyl, C3-C30 alkynyl, C 6 -Cj 4 aryl, C 7 -C 3 o arylalkyl, C8-C30 arylalkenyl, C 8 -C3o arylalkynyl, C3-C30 alkylester, C 7 -C15 arylester, Q-C30 alkylarylester, C 4 -C 3 o alkenylester, C4-C30 alkynylester, NH 2 , C2-C30 alkylamino, C 6 -Ci 4 arylamino, C 7 -C 3 o (arylalkyl)amino, C3-C30 alkenylamino, C3-C30 alkynylamino, C 8 -C 30 (arylalkenyl)
  • the D units for the (D 2 Ar z ) n polymers can be of the ructures:
  • X is S, Se, O, or NR; x is 0 or 1 ; y is 0 or 1 ; and R, R 1 , R 3 , R 4 , and R s are independently H, Ci-C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 6 -Ci 4 aryl, C 7 -C 30 arylalkyl, C 8 -C 30 arylalkenyl, C 8 -C 30 arylalkynyl, hydroxy, C 2 -C 3 o alkoxy, C 6 -C 14 aryloxy, C 7 -C 30 arylalkyloxy, C 2 -C 30 alkenyloxy, C 2 -C 30 alkynyloxy, C 8 -C 30 arylalkenyloxy, C 8 -C 30 arylalkynyloxy, C0 2 H, C 2 -C 30 alkylester, C 7
  • the Ar repeating units for the (D 2 Ar z ) n polymers are of the structure:
  • X' is NR', O, Se, or S;
  • R' is II, C C3o alkyl, C 2 -C 3 o alkenyl, C 2 -C 3 o alkynyl, C 6 -Ci 4 aryl, C7-C30 arylalkyl, C8-C 3 0 arylalkenyl, C8-C30 arylalkynyl, C 1 -C30 hydroxyalkyl, C 6 -Ci4 hydroxyaryl, C7-C30 hydroxyarylalkyl, C3-C 30 hydroxyalkenyl, C 3 -C3 0 hydroxy alkynyl, C8-C30 hydroxyarylalkenyl, Cg-C 3 o hydroxyarylalky
  • the (D 2 Ar z ) n polymer has D unit that are dioxythiophenes, above, and Ar units that include, for example, dioxyselenophenes, dioxypyrroles, or dioxyfurans, but do not include dioxythiophenes, where the Ar units can be of the structures above and/or the structure:
  • X is Se, O, or NR y is 0 or 1 ; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently H, C1-C30 alkyl, C 2 -C 3 o alkenyl, C 2 -C 30 alkynyl, C 6 -C ]4 aryl, C 7 -C 30 arylalkyl, C 8 -C 30 arylalkenyl, Cg-C 30 arylalkynyl, hydroxy, C 2 -C 3 o alkoxy, C 6 -C 14 aryloxy, C7-C30 arylalkyloxy, C 2 -C 3 o alkenyloxy, C2-C30 alkynyloxy, C 8 -C 30 arylalkenyloxy, C -C 3 o arylalkynyloxy, C0 2 H, C 2 -C 3 o alkylester
  • the dioxyselenophene, dioxypyrrole, or dioxyfuan When combined with other Ar units the dioxyselenophene, dioxypyrrole, or dioxyfuan may be unsubstituted or substituted, or absent other Ar units the dioxyselenophene, dioxypyrrole, or dioxyfuan are substituted on at least one of the carbons a to the oxygen.
  • the Ar repeating units for the (D 2 Ar z ) n polymers can be of the structures above and/or the structure:
  • R, R 9 and R 10 are independently C 3 -C 3 o alkyl, C3-C30 alkenyl, C 3 - C 30 alkynyl, C 6 -C) 4 aryl, C 7 -C 30 arylalkyl, C 8 -C 3 o arylalkenyl, C 8 -C 3 o arylalkynyl, C 3 -C 30 alkylester, C 7 -C i s arylester, Q-C30 alkylarylester, C 4 -C 3 o alkenylester, C4-C30 alkynylester, NH 2 , C2-C30 alkylamino, C 6 -Ci4 arylamino, C 7 -C 3 o (arylalkyl)amino, C3-C30 alkenylamino, C 3 -C 3 o alkynylamino, C 8 -C
  • the fully conjugated polymeric sequence is a portion of a random copolymer.
  • the fully conjugated polymeric sequence is a portion of a block, graft, branched, hyperbranched, or dendritic copolymer.
  • the fully conjugated polymeric sequence is a portion of a network.
  • the conjugated polymer or a polymeric precursor of the conjugated polymer can be soluble in at least one solvent. Exemplary solvents that can be employed are toluene, chloroform, dichloromethane, hexanes, tetrahydrofuran, chlorobenzene, water, ethanol, xylene, tetralin, or mesitylene.
  • the conjugated polymer can be as a thin film where in the neutral state displays a lambda max between 400 nm and 500 nm and greater than about 90% transmittance from 600 nm-750 nm.
  • the thin film comprising the conjugated polymer in the oxidized state is color neutral having an a* of no greater than +/- 10 and b* of no greater than +/- 10.
  • the conjugated polymer can be electroclxromic or electroluminescent.
  • the conjugated polymer can have the structure: PAcDOT 2 -Ph(OMe) 2 , PProDOT 2 -Ph(OMe) 2 , or PAcDOT 2 /PProDOT 2 -Ph(OMe) 2 ,
  • a conjugated polymer has a (DAr z ) n fully conjugated polymeric sequence of a donor (D) repeating unit selected from alkylenedioxyheterocycle having substituents on the alkylene carbons a to the oxygen alternating with one to three aromatic (Ar) repeating unit comprising aromatic hydrocarbons, thiophene, furan, pyrrole, selenophene, and any combination thereof, the Ar repeating unit having at least one substituent of at least 5 atoms on a carbon a to the carbon attached to an adjacent D repeating unit of the conjugated polymer, wherein n is 6 to 10,000, and wherein the conjugated polymer is yellow or orange in its neutral state and having an absorption maximum between 300 and 500 nm that upon oxidation is color neutral having an a* of no greater than +/- 10 and b* of no greater than +/- 10.
  • the D repeating units for the (DAr) n polymers are of the structure:
  • X is S; x is 0 or 1 ; y is 0 or 1 ; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently H, Ci-C 30 alkyl, C 2 -C 30 alkenyl, C2-C30 alkynyl, C 6 -C ]4 aryl, C7-C30 arylalkyl, C 8 -C 3 o arylalkenyl, C 8 -C 3 o arylalkynyl, hydroxy, C 2 -C30 alkoxy, C 6 -Ci4 aryloxy, C 7 -C30 arylalkyloxy, C 2 -C30 alkenyloxy, C2-C30 alkynyloxy, C S -C30 arylalkenyloxy, C 8 -C 3 o arylalkynyloxy, CO2H, ' C 2 -C30 alkyle
  • the D units for the (D 2 Ar z ) n polymers can be of the structures:
  • X is S, Se, O, or NR; x is 0 or 1; y is 0 or 1 ; and R, R 1 , R 3 , R 4 , and R 5 are independently H, C 1 -C30 alkyl, C2-C30 alkenyl, C 2 -C 30 alkynyl, C 6 -Ci4 aryl, C7-C30 arylalkyl, C 8 -C3o arylalkenyl, C 8 -C3o arylalkynyl, hydroxy, C2-C30 alkoxy, C 6 -Ci 4 aryloxy, C7-C30 arylalkyloxy, C2-C30 alkenyloxy, C2-C30 alkynyloxy, C 8 -C 30 arylalkenyloxy, C 8 -C3o arylalkynyloxy, C0 2 H, C 2 -C 3 o alkylester, C7-C 15 arylester
  • the (DAr z ) n polymer has D unit that are dioxythiophenes and Ar units that include, for example, dioxyselenophenes, dioxypyrroles, or dioxyfurans, but do not include dioxythiophenes, where the Ar units can be of the structures above and/or the structures:
  • X is Se, O, or NR y is 0 or 1 ; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently H, C 1 -C30 alkyl, C 2 -C30 alkenyl, C2-C30 alkynyl, C 6 -Ci4 aryl, C7-C30 arylalkyl, C8-C30 arylalkenyl, C8-C30 arylalkynyl, hydroxy, C 2 -C30 alkoxy, C 6 -Ci 4 aryloxy, C 7 -C 3 o arylalkyloxy, C 2 -C30 alkenyloxy, C 2 -C 3 o alkynyloxy, C8-C30 arylalkenyloxy, C8-C 30 arylalkynyl oxy, CO2H, C2-C30 alkylester, C7-C 15 aryle
  • the dioxyselenophene, dioxypyrrole, or dioxyfuan When combined with other Ar units the dioxyselenophene, dioxypyrrole, or dioxyfuan may be unsubstituted or substituted, or absent other Ar units the dioxyselenophene, dioxypyrrole, or dioxyfuan are substituted on at least one of the carbons a to the oxygen.
  • the additional Ar repeating units for the (D 2 Ar z ) n polymers can include repeating units of the structure:
  • X is Se, O, or NR;
  • R, R 9 and R 10 are independently C 3 -C 30 alkyl, C3-C30 alkenyl, C3-C30 alkynyl, C6-C
  • Embodiments of the invention are directed to the preparation of the above conjugated polymers where the method comprises a cross-coupling of monomers or trimers.
  • the cross- coupling can be a direct arylation, Stille coupling, Kumada coupling, Hiyama coupling, Negishi coupling, inverse Suzuki coupling, Grignard methathesis (GRIM) or oxidative polymerization.
  • GRIM Grignard methathesis
  • electrochromic devices can include the above conjugated polymer and include at least one non-yellow or non-orange conjugated polymer that displays a primary subtractive color in a neutral state and is color neutral in an oxidized state.
  • the combined ECPs can include non-yellow conjugated polymers that display red and blue in the neutral state.
  • the combined ECPs can include non-yellow conjugated polymers that display magenta and cyan in the neutral state.
  • FIG. 1A shows an L*a*b* color wheel with the high bandgap color space demarcated
  • FIG. IB shows a representative UV-Vis-NIR spectra of a high gap polymer in its charge neutral state, ECP° (solid line), and oxidized state, ECP + (dashed line).
  • FIG. 2 shows contrasting structures for low redox stability state of the art high gap polymers, top line, and more redox stable high gap polymers, bottom line, according to an embodiment of the invention.
  • FIG. 3 shows absorbance spectra of poly(l,3-dimethyIProDOT- /t-3,4- dioctylthiophene) tangerine ECP, according to an embodiment of the invention, in its fully colored and bleached states when immersed in 0.5 M TBAP1VPC.
  • FIG. 4 shows the transmittance measured at 464 nm of films of poly(l ,3- dimethylProDOT-a//-3,4-dioctylthiophene) in its fully oxidized and neutral states over the course of 1000 redox switches. Films were switched in 0.5 M TBAPF 6 /PC with repeated square-wave potential steps, holding for 5 s in the oxidized and neutral states.
  • FIG. 5A shows a synthetic scheme for the preparation of PAcDOT 2 -Ph(OMe) 2 , PProDOT 2 -Ph(OMe) 2 , and PAcDOT 2 /ProDOT 2 -Ph(OMe) 2 using direct arylation polymerization, according to an embodiment of the invention.
  • FIG. 5B shows a synthetic scheme for the preparation of PEDOT-DAT 2 using direct arylation polymerization, according to an embodiment of the invention.
  • FIG. 6 shows the neutral state spectra of high bandgap ECP films, according to an embodiment of the invention, on ITO-coated glass in 0.5 M TBAPF 6 /PC electrolyte solution for films sprayed to an absorbance of 1.00 ⁇ 0.03.
  • FIG. 7A shows the absorbance spectroelectrochemistry of PAcDOT 2 -Ph(OMe) 2 , according to an embodiment of the invention, where applied potential, as shown by the arrow, was increased in 10-50 mV steps between the fully colored and bleached states in 0.5 M TBAPF 6 /PC.
  • FIG. 7B shows the absorbance spectroelectrochemistry of PProDOT 2 -Ph(OMe) 2 , according to an embodiment of the invention, where applied potential, as shown by the arrow, was increased in 10-50 mV steps between the fully colored and bleached states in 0.5 M TBAPF 6 /PC.
  • FIG. 7C shows the absorbance spectroelectrochemistry of PAcDOT 2 /ProDOT 2 - Ph(OMe) 2 , according to an embodiment of the invention, where applied potential, as shown by the arrow, was increased in 10-50 mV steps between the fully colored and bleached states in 0.5 M TBAPF 6 /PC.
  • FIG. 7D shows overlaying transmittance spectra (%) of the oxidized forms of PProDOT-Ph, PAcDOT 2 -Ph, PProDOT 2 -Ph, PAcDOT 2 -Ph(OMe) 2 , PProDOT 2 -Ph(OMe) 2 , and PAcDOT 2 /ProDOT 2 -Ph(OMe) 2 for films spray-cast onto ITO coated glass to an absorbance of 1.00 ⁇ 0.03, according to an embodiment of the invention.
  • FIG 8B shows photographs of the fully neutral and fully oxidized films of the yellow and orange ECPs according to embodiments of the invention.
  • FIG. 9B shows the chronoabsorptometry of PProDOT 2 -Ph(OMe) 2 in 0.5 M TBAPF 6 /PC electrolyte solution measured at 500 nm from -0.5 to 0.7 V vs. Ag/Ag + .
  • FIG. 9C shows the chronoabsorptometry of PAcDOT 2 /ProDOT 2 -Ph(OMe) 2 in 0.5 M TBAPF 6 /PC electrolyte solution measured at 476 nm from -0.5 to 0.75 V vs. Ag/Ag + .
  • FIG. 10 shows the transmittance measured at a single wavelength for films of PAcDOT 2 -Ph(OMe) 2 , PProDOT 2 -Ph(OMe) 2 and PAcDOT 2 /ProDOT 2 -Ph(OMe) 2 switched between their neutral and fully oxidized states. The time to reach 95% of the full optical contrast upon bleaching and coloration are indicated..
  • FIG. 1 1 shows plots of contrast loss versus number of switching cycles in 0.5 M
  • embodiments of the invention are directed to yellow or orange-to-transmissive switching cathodically coloring ECPs, their preparation, and displays having a palette of subtract! ve colors including the neutral state yellow or orange conjugated polymer.
  • the yellow conjugated polymers exhibit high optical contrasts at the wavelength of peak absorption in the neutral state, which upon oxidation become highly transmissive throughout the entire visible region.
  • the yellow and orange conjugated polymers are soluble in at least one solvent, for example toluene, chloroform, dichloromethane, hexanes, tetrahydroiuran, chlorobenzene, water, ethanol, other solvents or combination of solvents.
  • yellow-to-transmissive or orange-to- transmissive conjugated polymers can be included in either reflective or transmissive ECDs which use conjugated polymers of three primary colors, either red, yellow and blue (RYB) or cyan, magenta and yellow (CMY), in a complete subtractive color space to allow any color to be produced by the appropriate color combination.
  • the yellow-to-transmissive or orange-to-transmissive conjugated polymers can be included in a thin film with complementary colors to yield a black neutral state device and a transmissive oxidized state.
  • These complete multicolor conjugated polymer devices can be used in various display technologies such as displays for electronics, full color e-books, and signage.
  • electroluminescent or combination electroluminescent/ electrochromic devices are formed, having light emitting and/or electrochromic properties.
  • the yellow and orange conjugated polymers are transmissive and color neutral in the oxidized state and yellow or orange in a neutral state with peak absorption, max , at about 450 nm to about 500 nm, where as a thin film, the yellow or orange conjugated polymers display less than 20% transmission at peak absorption, and having an onset of absorption of 2.1-3.0 eV in the neutral state and can be converted by electrochemical reaction to a film with greater than 70% transmission throughout the visible spectrum from 400-750 nm.
  • the yellow and orange conjugated polymers display high optical contrast in the visible region, possess rapid switching speeds, and good stability upon repetitive switching.
  • the yellow conjugated polymers can be processed from solution, which is advantageous for use in reflective and transmissive electrochromic devices (ECDs), electroluminescent devices, or combination electroluminescent/electrochromic devices.
  • ECP- Yellow- 1 By increasing the strain imposed upon the backbone by steric features of the repeating units the color can be tuned and the oxidation potential required for switching can be diminished.
  • state of the art ECP- Yellow- 1 shown below, can be modified from the alternating copolymer of an alkylene-dioxythiophene-arylene (DAr) n to a copolymer ECP-Yellow-2, according to an embodiment of the invention, shown below, where the decreased steric requirements of the ECP-Yellow-2 leads to a lower oxidation potential.
  • Dr alkylene-dioxythiophene-arylene
  • PAcDOT 2 -Ph exhibited a 5% decrease in contrast ( ⁇ % ⁇ ) over a hundred switches resulting in a decrease in the vibrancy of the colored state, compared with PProDOT homopolymer, which is stable over tens of thousands or more switches.
  • donor D units for the (D 2 Ar 7 ) n polymers are of the structure:
  • X is S, Se, O, or NR; x is 0 or 1 ; y is 0 or 1 ; and R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently H, C 1 -C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C6-Ci 4 aryl, C7-C30 arylalkyl, C 8 -C 30 arylalkenyl, C 8 -C 3 o arylalkynyl, hydroxy, C 2 -C 3 o alkoxy, C -CH aryloxy, C 7 - C 30 arylalkyloxy, C 2 -C3o alkenyloxy, C?-C3o alkynyloxy, C8-C30 arylalkenyloxy, C8-C30 arylalkynyloxy, C0 2 H, C 2 -C3
  • Alkyl groups can be straight, branched, multiply branched, cyclic, or polycyclic where cyclic and polycyclics can be unsubstituted, substituted, or polysubstituted, alkenyl can be a monoene, conjugated or non-conjugated polyene, straight, branched, multiply branched, cyclic, or polycyclic, terminal or internal, substituted at any carbon, E or Z isomers or mixture thereof, alkynes can be mono-yne, conjugated or non-conjugated poly-yne, terminal or internal, substituted at any carbon, aryl groups can be cyclic, fused or unfused polycyclic of any geometry, asymmetric functional groups, such as ester and amido, can have either orientation with respect to the
  • poly can be 2 or more.
  • Heteroatoms in substituents R -R can be at any position of those substituents.
  • an oxygen of an ether or ester or a nitrogen of an amine or amide can be in the alpha, beta, gamma or any other position relative to the point of attachment to the 3,4-alkylenedioxythiophene.
  • Heteroatom containing substituents can have a plurality of heteroatoms, for example, ether can be a monoether, a diether or a polyether, amine can be a monoamine, a diamine or a polyamine, ester can be a monoester, a diester, or a polyester, and amide can be a monoamide, a diamide or a polyamide.
  • Ether and ester groups can be thioethers, thioesters and hydroxy groups can be thiol (mercapto) groups, where sulfur is substituted for oxygen.
  • Salts can be those of alkali or alkali earth metals, ammonium salts, or phosphonium salts.
  • the D units for the (D2Ar z ) n polymers can be of the
  • X is S, Se, O, or NR; x is 0 or 1 ; y is 0 or 1 ; and R, R 1 , R 3 , R 4 , and R 3 are independently H, Ci-C 30 alkyl, C 2 -C30 alkenyl, C 2 -C 30 alkynyl, C 6 -Cj4 aryl, C7-C30 arylalkyl, C8-C30 arylalkenyl, C8-C30 arylalkynyl, hydroxy, C 2 -C 3 o alkoxy, C 6 -Ci4 aryloxy, C7-C30 arylalkyloxy, C 2 -C 3 o alkenyloxy, C 2 -C30 alkynyloxy, Cg-C 3 o arylalkenyloxy, C 8 -C3o arylalkynyloxy, C0 2 H, C 2 -C 30 alkylester, C 7
  • donor D units for the (D 2 Ar z ) n polymers can be of the structure:
  • R, R 9 and R 10 are independently C3-C30 alkyl, C3-C30 alkenyl, C3-C30 alkynyl, C 6 -Ci 4 aryl, C7-C30 arylalkyl, C8-C30 arylalkenyl, C8-C30 arylalkynyl, C 3 -C 30 alkylester, C7-C 15 arylester, C 8 -C 30 alkylarylester, C 4 -C3o alkenylester, C4-C30 alkynylester, NH 2 , C2-C30 alkylamino, C 6 -Ci 4 arylamino, C 7 -C 30 (arylalkyl)amino, C3-C30 alkenylamino, C3-C30 alkynylamino, C 8 -C 3 o (arylalkenyl)amino, C
  • Alkyl groups can be straight, branched, multiply branched, cyclic, or polycyclic where cyclic and polycyclics can be unsubstituted, substituted, or polysubstituted, alkenyl can be a monoene, conjugated or non-conjugated polyene, straight, branched, multiply branched, cyclic, or polycyclic, terminal or internal, substituted at any carbon, E or Z isomers or mixture thereof, alkynes can be mono-yne, conjugated or non-conjugated poly-yne, terminal or internal, substituted at any carbon, aryl groups can be cyclic, fused or unfused polycyclic of any geometry, asymmetric functional groups, such as ester and amido, can have either orientation with respect to the 3,4- dioxythiophene rings, poly can be 2 or more.
  • Heteroatoms in substituents R 9 and R 10 can be at any reasonable position of those substituents.
  • an oxygen of an ether or ester or a nitrogen of an amine or amide can be in the beta, gamma or any other position relative to the point of attachment to the 3,4-dioxythiophene, but not the alpha position.
  • Heteroatom containing substituents can have a plurality of heteroatoms, for example ether can be a monoether, a diether or a polyether, amine can be a monoamine, a diamine or a polyamine, ester can be a monoester, a diester, or a polyester, and amide can be a monoamide, a diamide or a polyamide.
  • Ethers and esters groups can be thioethers, thioesters and hydroxy groups can be thiol (mercapto) groups, where sulfur is substituted for oxygen.
  • Salts can be those of alkali or alkali earth metals, ammonium salts, or phosphonium salts.
  • X' is NR', O, Se, or S; where R' is H, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C 6 -C 14 aryl, C7-C30 arylalkyl, Cg-C3o arylalkenyl, Cg-C 3 o arylalkynyl, C1 -C30 hydroxyalkyl, C 6 -Ci 4 hydroxyaryl, C7-C30 hydroxyarylalkyl, C 3 -C 30 hydroxyalkenyl, C3-C30 hydroxyalkynyl, Q-C30 hydroxyarylalkenyl, C8-C30 hydroxyarylalkynyl, C3-C30 polyether,
  • the (D 2 Ar 7 ) n polymer has D unit that are dioxythiophenes and Ar units that include, for example, dioxyselenophenes, dioxypyrroles, or dioxyfurans, but do not include dioxythiophenes, where the Ar units can be of the structures above and/or the structure:
  • X is Se, O, or NR y is 0 or 1 ; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently H, C,-C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 3 o alkynyl, C 6 -Ci 4 aryl, C7-C30 arylalkyl, C 8 -C 30 arylalkenyl, C 8 -C 3 o arylalkynyl, hydroxy, C 2 -C 30 alkoxy, C 6 -Ci 4 aryloxy, C7-C30 arylalkyloxy, C 2 -C 30 alkenyloxy, C 2 -C 30 alkynyloxy, C8-C30 arylalkenyloxy, C 8 -C 30 arylalkynyloxy, C0 2 H, C 2 -C 30 alkylester, C7-C
  • the dioxyselenophene, dioxypyrrole, or dioxyfuan When combined with other Ar units the dioxyselenophene, dioxypyrrole, or dioxyfuan may be unsubstituted or substituted, or absent other Ar units the dioxyselenophene, dioxypyrrole, or dioxyfuan are substituted on at least one of the carbons a to the oxygen.
  • the Ar repeating units for the (D 2 Ar z ) n polymers can be of the structures above and/or the structure:
  • R, R 9 and R 10 are independently C 3 -C 30 alkyl, C3-C30 alkenyl, C3-C30 alkynyl, C 6 -Ci4 aryl, C- -C30 arylalkyl, C 8 -C 3 o arylalkenyl, Cg-Cso arylalkynyl, C3-C30 alkylester, C7-C15 arylester, C 8 -C3o alkylarylester, C4-C30 alkenylester, C4-C30 alkynylester, NH 2 , C2-C30 alkylamino, C 6 -C i4 arylamino, C7-C30 (arylalkyl)amino, C3-C30 alkenylamino, C3-C30 alkynylamino, C8-C30 (arylalkenyl)amino, C 8 -C 3
  • FIG. 2 shows examples of low redox stability yellow/orange polymers in the top row and the high gap copolymers of 2,5-dimethoxy-l ,4-phenylene polymerized with a variety of DOTs, according to an embodiment of the invention.
  • the yellow ECP PAcDOT 2 -Ph(OMe) 2 the presence of the bulky electron-rich methoxy units a to the bonds directly in the polymer backbone on the phenylene ring increases the steric hindrance in the backbone and pushes the band gap to higher energy, which promotes a brighter yellow color, while its electron donating character lowers the oxidation potential.
  • a yellow or orange electrochromic polymer is an alternating copolymer of the structure (DAr z ) n where the Ar group has the structure:
  • the donor D units for the (DAr) n polymers are of the structure:
  • X is S, Se, O, or NR
  • x is 0 or 1
  • y is 0 or 1
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently H, C]-C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 6 -Ci 4 aryl, C7-C30 arylalkyl, C 8 -C 30 arylalkenyl, C 8 -C 3 o arylalkynyl, hydroxyl, C 2 -C 3 o alkoxy, C 6 -Ci 4 aryloxy, C 7 -C 3 o arylalkyloxy, C 2 -C 3 o alkenyloxy, C 2 -C 3 o alkynyloxy, C 8 -C 30 arylalkenyloxy, C 8 -C 3 o arylalkyn
  • Alkyl groups can be straight, branched, multiply branched, cyclic, or polycyclic where cyclic and polycyclics can be unsubstituted, substituted, or polysubstituted, alkenyl can be a mono-ene, conjugated or non-conjugated polyene, straight, branched, multiply branched, cyclic, or polycyclic, temiinal or internal, substituted at any carbon, E or Z isomers or mixture thereof, alkynes can be mono-yne, conjugated or non-conjugated poly-yne, terminal or internal, substituted at any carbon, aryl groups can be cyclic, fused or unfused polycyclic of any geometry, asymmetric functional groups, such as ester and amido, can have either orientation with respect to the alkylenedioxythiophene rings, poly can be 2 or more.
  • Heteroatoms in substituents RZ -R 8 can be at any position of those substituents.
  • an oxygen of an ether or ester or a nitrogen of an amine or amide can be in the alpha, beta, gamma or any other position relative to the point of attachment to the 3,4-alkylenedioxythiophene.
  • Heteroatom containing substituents can have a plurality of heteroatoms, for example, ether can be a monoether, a diether or a polyether, amine can be a monoamine, a diamine or a polyamine, ester can be a monoester, a diester, or a polyester, and amide can be a monoamide, a diamide or a polyamide.
  • Ethers and esters groups can be thioethers, thioesters and hydroxy groups can be thiol (mercapto) groups, where sulfur is substituted for oxygen.
  • Salts can be those of alkali or alkali earth metals, ammonium salts, or phosphonium salts.
  • the D units for the (D2Ar z ) arena polymers can be of the
  • X is S, Se, O, or NR; x is 0 or 1 ; y is 0 or 1 ; and R, R 1 , R 3 , R 4 , and R 5 are independently H, C 1 -C30 alkyl, Q-C30 alkenyl, C 2 -C 3 o alkynyl, C 6 -Ci 4 aryl, C7-C30 arylalkyl, C8-C30 arylalkenyl, Cs-C 3 o arylalkynyl, hydroxy, C 2 -C3o alkoxy, C 6 -Ci4 aryloxy, C7-C30 arylalkyloxy, C 2 -C3o alkenyloxy, C 2 -C 3 o alkynyloxy, Cs-C 3 o arylalkenyloxy, C8-C30 arylalkynyloxy, C0 2 H, C 2 -C3o alkylester,
  • All R 1 , R 3 , R 4 , and R 5 groups can be H provided that at least one of the Ar group has at least one substituent of at least 5 atoms on a carbon a to the carbon attached to an adjacent D repeating unit of the conjugated polymer.
  • Examples of the ECPs, according to embodiments of the invention include, but are not limited to
  • R is n-octyl ; R is n-octyl ⁇ an( j R is n-octyl
  • the D unit has a substituent at R and/or R and at least one of R 3 , R 4 , R 5 , R 6 , R 7 and R 8 that is on the carbon a to the oxygen is not H.
  • An exemplary (DAr) n copolymer, according to this embodiment of the invention, is ECP- Tangerine, shown below, which display the same absorbance maximum as PAcDOT 2 -Ph but has an orange color because of a slightly broader absorption profile.
  • ECP-Tangerine PProDOT-Th(Octyl) 2
  • PProDOT-Th(Octyl) 2 tangerine ECP has sufficient strain to achieve a vibrant orange color yet retains a low oxidation potential (colorless by 0.5 V vs. Fc/Fc + ), as shown in FIG. 3, comparable to that of ECP-Magenta and ECP-Cyan and with similar contrast 65% ⁇ for ECP-Tangerine, vs ECP-Magenta 70% ⁇ and ECP-Cyan 50% ⁇ .
  • the stability is enhanced, exhibiting minimal loss in contrast when switched between its fully colored and colorless states for 1000 cycles for a thin film, in 0.5 M TBAPF 6 -propylene carbonate, as shown in FIG. 4.
  • the (D 2 Ar z ) n polymer has D unit that are alkylenedioxythiophenes, as indicated above, and Ar units that include, for example, dioxyselenophenes, dioxypyrroles, or dioxyfurans, but do not include dioxythiophenes, where the Ar units can be of the structures above and/or the structure:
  • X is Se, O, or NR y is 0 or 1 ; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R s are independently H, C1 -C30 alkyl, C 2 -C 3 o alkenyl, C2-C30 alkynyl, C 6 -C] 4 aryl, C7-C30 arylalkyl, C 8 -C 3 o arylalkenyl, C8-C 30 arylalkynyl, hydroxy, C 2 -C 30 alkoxy, C 6 -C i4 aryloxy, C 7 -C 30 arylalkyloxy, C 2 -C 30 alkenyloxy, C 2 -C 30 alkynyloxy, Cs-C 30 arylalkenyloxy, C 8 -C 30 arylalkynyloxy, C0 2 H, C 2 -C 30 alkylester, C7
  • the Ar repeating units for the (D2Ar z ) n polymers can be of the structures above and/or the structure:
  • R 9 and R 10 are independently C3-C30 alkyl, C3-C30 alkenyl, C3-C30 alkynyl, C 6 -C 14 aryl, C 7 -C30 arylalkyl, Q-C30 arylalkenyl, C8-C30 arylalkynyl, C3-C30 alkylester, C7-C 15 arylester, Cg-C3o alkylarylester, C4-C30 alkenylester, C4-C30 alkynylester, NH 2 , C2-C30 alkylamino, C 6 -Ci 4 arylamino, C7-C30 (arylalkyl)amino, C3-C30 alkenylamino, C3-C30 alkynylamino, C 3 ⁇ 4 -C 3 o (arylalkenyl)amino, C8-C30 (arylalkynyl)amino, C3-
  • the yellow or orange high gap conjugated polymer sequence is a portion of a block copolymer, graft copolymer, or polymer network where non- conjugated polymer portion(s) can be any polymer that can be prepared by a step-growth or chain-growth process.
  • non- conjugated polymer portion(s) can be any polymer that can be prepared by a step-growth or chain-growth process.
  • a triblock copolymer can be formed where a non-coloring polymer mono-terminated with either or both of the alternating units can be employed as end-capping monofunctional units in a condensation polymerization with a plurality of difunctional monomers for the yellow conjugated polymer's alternating sequence containing portion according to an embodiment of the invention.
  • a non-conjugated polymer in another embodiment, can be terminated at both ends with one of either of the monomers for the high gap EC portion to form a multiblock polymer upon condensation with the appropriate proportions of the two monomers for the yellow conjugated polymer portion.
  • a non-conjugated polymer with substitution of one of the complementary monomers of the conjugated polymer portion can be condensed with yellow conjugated polymer forming monomers to yield graft-like or network copolymers.
  • the yellow conjugated polymer segments can be formed before, during or after the formation of the non- conjugated polymer portion of block copolymers, as can be appreciated by one skilled in the art.
  • the yellow or orange high gap ECP can be transformed into a different polymer, by reactions on the conjugated polymer portion.
  • the reaction can be a transformation of the substituents on one or more of the alternating repeating units.
  • the yellow conjugated polymer can contain, for example, a reactive ProDOT of structure, as shown in structure I above, where R 1 through R 6 groups permit processing of the yellow conjugated polymer into a film that can be subsequently converted to a different yellow conjugated polymer and, for example, a soluble film can be converted into an insoluble film.
  • R 3 and R 4 are di-ester groups
  • conversion to carboxylic acid groups can be carried out in the manner disclosed in Reynolds et al. U.S. Patent No. 7,799,932, September 21, 2010, and incorporated by reference herein.
  • the di-acid can be subsequently converted into a carboxylate salt.
  • Reactions can also involve one or more units of the other polymeric segments of block copolymers other than those of the conjugated polymer portion.
  • Repeating units or terminal ends of the yellow conjugated polymer can be substituted to promote self associate or cross-associate with plurally functional additives to form a super- molecular structure through non-covalent interactions such as hydrogen bonding, ion-dipole, ion pairing, ion chelation, dipole-dipole, or other non-covalent bonding forces.
  • some repeating units may be substituted with specific polyol groups that are readily solvated by a solvent, but strongly associate specifically with one or more other polyol groups of the yellow conjugated polymer or of an additive upon removal of the solvent to form a super- molecular yellow conjugated polymer complex.
  • the polymer having a yellow conjugated polymer portion can be cross-linked, for example after deposition on a surface that will be part of a device, for example, an electrochromic device.
  • repeating units of the polymer can have a functional group that can be induced to add to or condense with another group upon activation or initiation that is within the conjugated polymer or on a reagent that is difunctional or polyfunctional that is added to the yellow conjugated polymer.
  • vinyl units can be induced to undergo vinyl addition
  • cyclic groups can be induced to undergo ring-opening addition
  • complementary groups can undergo catalyzed addition or condensation to form a network. Functionalities that can be employed can be appreciated by those skilled in the art.
  • a precursor to a yellow conjugated polymer network can be deposited on a surface from solution and a catalyst, a reagent, heat or radiation can be used to cause network formation.
  • a precursor to a yellow conjugated polymer network is a non-network yellow conjugated polymer according to an embodiment of the invention.
  • n yellow or orange high gap ECP are prepared by cross-coupling reactions of an electrophilic 3,4-alkylenedioxythiophene substituted on the alkylene bridge (I) or 3,4-dialkoxythiophene unit (II) and a nucleophilic aromatic donor unit.
  • This allows sufficient molecular weight where the fully conjugated limit of the ⁇ to ⁇ * transition is reached and the polymer can be solution processable as a yellow or orange film because reliable purifications of the nucleophilic monomer and the electrophilic monomer can be effectively carried out.
  • the degree of polymerization is limited by any deviation from stoichiometry.
  • the electrophilic monomers are substituted with leaving groups such as halogens, triflates, tosylates, mesylates, nosylates, trifluoroacetates or other substituted sulfonates that can act as the leaving group.
  • the nucleophilic monomers can be substituted with tin or zinc moieties rather than boron moieties.
  • Coupling reactions that can be used for the preparation of the yellow conjugated polymers, include, but are not restricted to: Suzuki coupling, Stille coupling, Kumada coupling, Hiyama coupling, Negishi coupling, direct arylation (DA) polymerization, Grignard methathesis (GRIM) and oxidation polymerization.
  • Suzuki coupling Stille coupling
  • Kumada coupling Kumada coupling
  • Hiyama coupling Hiyama coupling
  • Negishi coupling direct arylation (DA) polymerization
  • GRIM Grignard methathesis
  • the yellow or orange ECP can have tuned electrochromic features that permit a desired device fabrication method.
  • the substituents comprise non-polar side chains.
  • the substituents comprise polar or ionic side chains, including but not exclusive to: ether, ester, amide, carboxylic acid, sulfonate, and amine functionalized chains.
  • the yellow conjugated polymers can be designed to adsorb on metal or metal oxide surfaces, for example, but not limited to, titania, for use in dye sensitized solar cells (Graetzel Cells) or other devices.
  • An electrochromic device can be formed by a layer-by-layer deposition process when a substituent that imparts solubility to the yellow or orange ECP is included with one or more other conjugated polymers that provide one or more different colors.
  • an ECD displays all colors by the subtractive color mixing of Cyan Magenta Yellow (CMYK) or Red Yellow Blue (RYB) conjugated polymers employing the yellow conjugated polymer, according to an embodiment of the invention.
  • the desired colors can be achieved by: sequentially patterning the multiple colors (CMY or RYB) in a layered fashion to achieve color mixing; patterning in a lateral configuration, such that the patterned pixels are small enough and close enough that the human eye sees the adjacent colors as a mixture; or stacking as films on separate electrodes to mix colors.
  • the polymers of colors red, yellow, and blue can be patterned as clusters of squares, rectangles, circles, triangles, or other regular or irregular shapes, onto patterned electrode pixels to combine the colors at each pixel and allow the resulting observed color to be any color of the visible spectrum.
  • the pixel displays the color orange, and, when the yellow and blue pixels are in the neutral state with the red pixel in a colorless oxidized state, the displayed color is green.
  • the yellow or orange ECPs according to embodiments of the invention can be employed in a wide variety of applications.
  • the ECPs can be a component of an active layer in bulk heteroj unction solar cells.
  • the R groups of the 3,4-dialkoxythiophene unit can be of a structure that directs and enhances adsorption of the yellow conjugated polymer to a metal oxide through a polar carboxylate or even phosphate functionalities for use in dye sensitized solar cells, where the yellow EC polymer functions as the active light absorbing layer.
  • Other uses for the yellow or orange ECPs, according to embodiments of the invention are as charge transport layers and charge injection layers for field-effect transistor devices.
  • PAcDOT 2 -Ph(OMe) 2 , PProDOT 2 - Ph(OMe) 2 , and PAcDOT 2 /ProDOT 2 -Ph(OMe) 2 were prepared by direct arylation (DA) polymerization as illustrated in FIG. 5A.
  • PEDOT-DAT 2 was polymerized as shown in FIG. 5B. All the dimethoxyphenylene-based copolymers were obtained in high yields (> 70%), with number average molecular weights (Mi) ranging from 24.1 to 60.2 kDa, and dispersities (£>) ranging from 1.7 to 2.3 after Soxhlet extraction.
  • All three polymers are highly soluble (> 10 mg/mL) in common organic solvents including chloroform, THF, and toluene owing to the ethylhexyloxy chains on the DOT units.
  • the thermal stability of the polymers was studied by TGA and found to be stable up to 320°C.
  • Oxidative polymerization was also carried out using AcDOT2-Ph(OMe) 2 with excess FeCl 3 in ethyl acetate at room temperature, and resulted in PAcDOT 2 -Ph(OMe)2 with a M n of 1 1.7 kDa and a dispersity of 3.9, but led to low yields around 20%, likely due to a large fraction of low molecular weight oligomers.
  • Electrochemical and Optical Properties of High-Gap ECPs The polymers in Scheme 1 possess various structural motifs that readily allow for fine-tuning of the optical and electronic properties. Variation of the arylene and DOT units to tune the electron- richness and/or the steric strain along the polymer backbone affects the onset of oxidation (E ox ) as shown in Table 1 and in the differential pulse voltammetry (DPV) results. By increasing the number of electron-rich DOTs in the repeat unit, the E ox is substantially lowered. The addition of a second ProDOT unit in PProDOT 2 -Ph lowers the E ox by 260 mV compared to PProDOT-Ph.
  • redox and absorbance profiles do not appear to be simply an overlap from those of the parent polymers, indicating that the film properties are derived from the novel AcDOT 2 -Ph(OMe) 2 -ProDOT 2 -Ph(OMe)2 repeat units indicating that redox and optical properties can be readily modified by adjusting the ratio of AcDOT and ProDOT along the copolymer backbone.
  • PProDOT 2 -Ph(OMe) 2 1 26 500 2. 1 5 PAcDOT 2 -Ph 438 464 2.27
  • the optical properties of polymer solutions and spray-cast thin films are shown in FIG.6.
  • PAcDOT 2 -Ph(OMe) 2 has a higher band gap than PAcDOT 2 -Ph, however PProDOT 2 - Ph(OMe) 2 has a lower band gap than PProDOT 2 -Ph.
  • the AcDOT comprising ECPs with relatively bulky and electron-rich methoxy units in place of the smaller hydrogen atom on the phenylene ring has a significant effect on the backbone planarity/sterics because the side- chains on the AcDOTs extend along the plane of the backbone, which can interact with the methoxy groups.
  • the resulting torsional strain along the backbone causes a decrease in conjugation, with an accompanying increase in the band gap giving rise to a more yellow color.
  • the addition of the methoxy groups play a smaller role in steric interactions as the side-chains are not only located further from the methoxy groups but they are also orthogonal to the plane of the backbone and, as a result, do not interact with them to a high degree.
  • the electron -richness of the methoxy groups also affect the HOMO and lower the band gap for PProDOT 2 -Ph(OMe) 2 relative to its unsubstituted analog. This demonstrates that the steric and electronic effects observed here are intertwined, and depend upon the neighboring groups present, and not just on the substituents themselves.
  • the switching properties of the polymer films are evaluated by monitoring the absorption changes upon electrochemical oxidation.
  • the spectra of the Ph(OMe) 2 -based polymers are shown in FIG. 7A.
  • the charge carrier bands for the PAcDOT-based ECPs are blue-shifted ( ⁇ ⁇ : 1400-1500 nm) compared to the ProDOT-analogs fX, max : >1700 nm, FIG. 7B and FIG. 7C).
  • the low energy charge carrier band is further red-shifted as a result of the incorporation of the electron-rich methoxy groups.
  • the PAcDOT 2 /ProDOT 2 -Ph(OMe) 2 displays a neutral state more closely resembling PAcDOT 2 -Ph(OMe) 2 but an oxidized state resembling PProDOT 2 -Ph(OMe) 2 .
  • the charge carrier band between 700 and 800 nm is not particularly affected by the choice of DOT unit or the substitution pattern on the phenylene ring.
  • the maximum contrast and the quantified colors of the ECP films, according to embodiments of the invention, in the neutral and oxidized states is provided in Table 2, below.
  • PProDOT 2 -Ph(OMe) 2 exhibited the highest contrast (70 ⁇ % ⁇ at 500 nm) and the most transmissive oxidized state followed by the copolymer PAcDOT 2 /ProDOT 2 - Ph(OMe) 2.
  • PProDOT-Ph reaches a similar contrast as the copolymer if measured at max , however, across the visible spectrum the color neutrality is compromised by a residual absorbance at the long wavelength edge of the visible.
  • the lower contrast of the AcDOT-based polymers can be ascribed to the lower degree of planarity due to steric hindrance which makes it energetically more difficult to fully planarize upon electrochemical oxidation as well as a result of charge carrier bands that tail into the visible.
  • the contrast of the copolymer PAcDOT 2 /ProDOT 2 -Ph(OMe) 2 is higher than PAcDOT 2 -Ph(OMe) 2 , and only slightly lower than PProDOT 2 -Ph(OMe) 2 .
  • the contrast values at ). max increase with the incorporation of ProDOT units as the steric twist is reduced and the electron-richness increased.
  • PAcDOTrPn 51 87, 9, 76 87, 2, 4 PAcDOT 2 -Ph(OMe) 2 59 89 -4, 85 81, -1, -1
  • the colors of the ECPs can be quantified by converting the spectra into L*a*b* color coordinates where the L* represents the lightness-darkness of a given color, a* the red-green balance, and the b* the yellow-blue balance.
  • the L*a*b* coordinates for the neutral and oxidized states are summarized in Table 2.
  • FIG. 8A shows how the a*b* values of the respective polymers change upon electrochemical oxidation
  • FIG. 8B shows the photographs of the polymers in their fully colored and fully colorless states.
  • ProDOT-Ph, P AcDOT 2 -Ph and PAcDOT 2 -Ph(OMe) 2 all have a vibrant yellow color as confirmed by their low a* values and high b* values.
  • PAcDOT 2 -Ph(0]VIe) 2 is the purest yellow, having the highest b* and lowest a*. In addition to being the most vibrant yellow, it has the lowest oxidation potential of the three, 250 mV lower than ProDOT-Ph which is otherwise very similar in color.
  • the steric hindrance between chains is reduced, leading to a more relaxed backbone. This in turn causes the neutral state color of PProDOT 2 -Ph(OMe) 2 and ProDOT 2 -Ph to have a slightly red-shifted absorption profile translating into the colors having a substantial a* component, placing them in the orange color space.
  • FIG. 10 shows an overlap of the chronoabsorptometry curves during a 10 second switch.
  • the contrast ( ⁇ %7) of the films was monitored with repeated square- wave potential steps of 10 s, switching between the fully reduced and fully oxidized states for 100 cycles under ambient laboratory conditions.
  • FIG. 11 when comparing PAcDOT 2 - Ph(OMe) 2 with PAcDOT 2 -Ph, the presence of the methoxy units leads to an increase in redox stability, with the unsubstituted analog losing 20 % of contrast over the course of 100 cycles, while the methoxy-substituted analog loses 4 %.

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Abstract

Des modes de réalisation de l'invention portent sur des polymères conjugués jaunes/orangés à transmissifs, sur un procédé de préparation des polymères conjugués jaunes/orangés, et sur un dispositif électrochrome et/ou électroluminescent comprenant les polymères conjugués jaunes/orangés à l'état neutre, en tant que l'un d'une pluralité de polymères conjugués à couleur primaire soustractive. Les polymères conjugués jaunes/orangés présentent une stabilité rédox améliorée et peuvent avoir une structure (D2Arz)n, comprenant un motif répétitif dioxyhétérocyclique, ou une structure (DAr7)n comprenant un dioxythiophène monomère présentant au moins un carbone a substitué à un oxygène du monomère ; et les un à trois groupes Ar présentent au moins un carbone a substitué au carbone fixé au motif D, qui présente au moins 5 atomes dans le substituant. Les polymères conjugués jaunes/orangés présentent une stabilité rédox améliorée. Les polymères conjugués jaunes/orangés sont préparés par des réactions de condensation croisée.
PCT/US2017/048013 2016-08-22 2017-08-22 Polymères électrochromes jaunes et orangés à large bande interdite Ceased WO2018039230A1 (fr)

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